CN103756315B - A kind of compositions of thermosetting resin and application thereof - Google Patents
A kind of compositions of thermosetting resin and application thereof Download PDFInfo
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- CN103756315B CN103756315B CN201310703411.2A CN201310703411A CN103756315B CN 103756315 B CN103756315 B CN 103756315B CN 201310703411 A CN201310703411 A CN 201310703411A CN 103756315 B CN103756315 B CN 103756315B
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Abstract
The invention provides a kind of compositions of thermosetting resin, comprise the prepolymer of diallyl compound and maleimide compound, the structural formula of described diallyl compound as the formula (1):Wherein, R1For C (CH3)2、‑C(CF3)2、‑SO2、‑CH(CH3)、‑CH2Or oxygen atom；R2And R3For aliphatic group or the aryl radical of carbon number less than 30 of identical or different carbon number less than 10, and described R2And R3Do not comprise allyl group.This compositions of thermosetting resin has good heat stability and humidity resistance, dielectric constant and dielectric loss angle tangent are low and have excellent processes.The embodiment of the present invention additionally provides the application in resin sheet, resin laminated metal paper tinsel, prepreg, laminate, metal-clad laminate and printed wiring board of this compositions of thermosetting resin.
Description
Technical field
The present invention relates to a kind of resin combination, particularly relate to a kind of compositions of thermosetting resin and at resin sheet
Application in material, resin laminated metal paper tinsel, prepreg, laminate, metal-clad laminate and printed wiring board.
Background technology
In recent years, along with the development of information communication device high performance, multifunction and networking, for high-speed transfer
And processing Large Copacity information, operation signal trends towards high frequency, meanwhile, in order to meet the Developing Tendency important and influential persons of each electronic product
Asking, circuit board develops towards the direction of high multilamellar, high wiring density, and this just requires that baseplate material not only has good dielectricity
(low-k and low dielectric loss angle tangent) needs of signal high-frequency transmission can be met, and require to have good resistance to
Hot and machining property meets the demand of multilayer printed circuit board reliability and processability.
But existing in the material of tellite, binding agent based on epoxy resin is widely used.
The general dielectric constant of common epoxy resin circuit substrate (FR-4 copper-clad plate) and the higher (dielectric constant of dielectric loss angle tangent
4.4, dielectric loss angle tangent about 0.02), high frequency characteristics is insufficient, it is impossible to adapt to the requirement of signal high frequency.
The another kind of thermoplastic fluoroelastomer resinoid (politef) as baseplate material, although dielectric constant and dielectric loss
Angle tangent is low, but, fluorine-type resin its melt temperature general and melt viscosity are high, because its mobility is relatively low, have compressing
The problem that Shi Bixu is set in the condition of High Temperature High Pressure.And when making the printed circuit board (PCB) of high multilamellar, have processability, size steady
The problem points such as qualitative and with metal coating cementability is not enough.
In being that instead of fluorine-type resin, research is suitable for the resin material of the use in printed circuit board of high-frequency applications.Wherein, thermostability
Polymer attracts attention with the use of the excellent polyphenylene oxide resin of dielectric property.But, polyphenylene oxide be similarly melt temperature and
The thermoplastic resin that melt viscosity is high, because molecular weight is big, solution viscosity is big, and the problems such as melting viscosity is big exist a lot of challenges,
As needed for meeting electronic building brick low dielectric loss factor while be difficult to reach all electrical properties, anti-flammability and mechanicalness
Matter (such as thermostability, chemical resistance, high peel strength of copper foil, low-dielectric loss angle tangent and agent of low hygroscopicity).Additionally manufacturing
The manufacturability difference of the course of processing and processing difficulties, can cause scrappage increase, less reliable.
For obtaining the circuit board meeting hyundai electronics Information Technology Development needs, those skilled in the art has been carried out in a large number
Research work, reach optimum being expected to each side such as various performance, reliability, manufacture processability, but effect be not very
Preferable.Or obtain good dielectric properties or thermostability, but technological forming or poor in processability；Or manufacturability
Can improve, but the performance of itself is but deteriorated.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of compositions of thermosetting resin, existing in order to solve
In technology, compositions of thermosetting resin dielectric properties are poor, heat stability and wet-hot aging performance is poor, curing efficiency is low, processes
The problems such as difference.
First aspect, embodiments provides a kind of compositions of thermosetting resin, comprise diallyl compound with
The prepolymer of maleimide compound, the structural formula of described diallyl compound as the formula (1):
Wherein, R1For-C (CH3)2、-C(CF3)2、-SO2、-CH(CH3)、-CH2Or oxygen atom；R2And R3For identical or different
The aliphatic group of carbon number less than 10 or the aryl radical of carbon number less than 30, and described R2And R3Do not comprise pi-allyl
Group；
The general formula of molecular structure of described maleimide compound is as the formula (2):
In formula, R is aliphatic group or aromatic group, Xa、XbRepresent identical or different hydrogen atom, halogen atom and fat
One in fat race group, m represents the integer of 1 and more than 1.
The compositions of thermosetting resin that embodiment of the present invention first aspect provides, described diallyl compound and Malaysia
The prepolymer of imide compound is to be obtained by reaction with maleimide compound by diallyl compound.Such as formula (2)
Shown diallyl compound has the most volatile characteristic with the prepolymer of maleimide compound, it is ensured that thermosetting
The stability of component ratio in property resin combination, i.e. ensure that the stablizing of dielectric properties of compositions of thermosetting resin, and this is
Because the deviation of any component ratio all can cause the dielectric properties of compositions of thermosetting resin in compositions of thermosetting resin
Difference.It addition, described diallyl compound is little with the prepolymer molecule structural polarity of maleimide compound, therefore have
There are the most excellent dielectric properties, when the cross-linking agent as resin uses, compositions of thermosetting resin excellence can be given
The good performances such as dielectric properties, high-fire resistance, low water absorbable.3rd, described diallyl compound and maleimide
The prepolymer of compound has good solubility property, is difficult in the solution separate out, and has low-down melting viscosity, can
To give the manufacture processing characteristicies such as the good dipping of compositions of thermosetting resin, lamination.4th, described diallyl compound
With the prepolymer of maleimide compound because containing maleimide structure unit, the thermosetting containing this component can be given
The good fire resistance of circuit substrate that resin combination makes, low thermal coefficient of expansion (x, y, z to), good dimensional stability,
High elastic modelling quantity, it is easy to be fabricated to halogen-free copper-clad plate, IC support plate, meets fine-line, the processing of highly dense circuit.
Preferably, described R2And R3Independently selected from methyl, ethyl, propyl group, phenyl, naphthyl, bicyclic pentadiene, hexamethylene
Base, phenethyl, benzyl and to the one in ethenybenzyl.
Preferably, described R2And R3Independently selected from ethyl with to the one in ethenybenzyl.
Preferably, described diallyl compound is by described diallyl with the prepolymer of maleimide compound
Compound and described maleimide compound are 90 DEG C～170 DEG C in pre-polymerization temperature, and the pre-polymerization time is 10min's～1080min
Under the conditions of pre-polymerization obtain.
Preferably, described diallyl compound is by described diallyl with the prepolymer of maleimide compound
Compound and described maleimide compound 1:(0.05 in molar ratio～5) pre-polymerization forms.
Preferably, described diallyl compound is by described diallyl with the prepolymer of maleimide compound
Compound and described maleimide compound 1:(0.4 in molar ratio～2.5) pre-polymerization forms.
Preferably, described maleimide compound be selected from phenylmethane list maleimide, N-phenylmaleimide,
N-(2-aminomethyl phenyl) maleimide, N-(4-aminomethyl phenyl) maleimide, N-(2,6-3,5-dimethylphenyl) maleimide
Amine, N-(2,6-diethyl phenyl) maleimide, N-(2-methoxyphenyl) maleimide, diphenyl-methane bismaleimide
Amine, Diphenyl Ether Bismaleimide, diphenyl sulphone (DPS) BMI, N-benzyl maleimide, N-dodecyl maleimide
At least one in amine, N-isopropylmaleimide and N-N-cyclohexylmaleimide.
Preferably, described diallyl compound accounts for described thermosetting resin group with the prepolymer of maleimide compound
The 5%～70% of compound gross weight.
Preferably, described diallyl compound accounts for described thermosetting resin group with the prepolymer of maleimide compound
The 15%～55% of compound gross weight.
Preferably, described compositions of thermosetting resin comprises polyphenylene oxide resin, cyanate ester resin, BMI-three
Piperazine resin, 1, at least one thermosetting resin in 2-polybutadiene, butadiene styrene resin and BMI, described thermosetting
Property resin accounts for the 0%～95% of compositions of thermosetting resin gross weight.
Preferably, described polyphenylene oxide resin is the polyphenylene oxide resin in molecular structure containing unsaturated group, described insatiable hunger
It is vinyl, pi-allyl, acrylate-based or alkynyl with group.
Preferably, the polyphenylene oxide resin containing unsaturated group in described molecular structure accounts for compositions of thermosetting resin gross weight
The 10%～60% of amount.
Preferably, described compositions of thermosetting resin further includes machine additive flame retardant, described organic addition type
Fire retardant is phosphorus flame retardant and/or halogenated flame retardant.
Preferably, described compositions of thermosetting resin comprises filler and/or curing initiator further.
The compositions of thermosetting resin that embodiment of the present invention first aspect provides, has good heat stability and wet-heat resisting
Property, good toughness, dielectric constant and dielectric loss angle tangent are low, have the solidification temperature of less than 200 DEG C and shorter solidification
Time, and there is excellent processes.
Second aspect, embodiments provides the compositions of thermosetting resin that embodiment of the present invention first aspect provides
Application in resin sheet, resin laminated metal paper tinsel, prepreg, laminate, metal-clad laminate and printed wiring board.
The advantage of the embodiment of the present invention will partly illustrate, a part according to description be aobvious and
It is clear to, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is ethyl etherificate diallyl bisphenol and the diphenyl methane dimaleimide of the embodiment of the present invention 1 synthesis
The infrared spectrogram of prepolymer.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvements and modifications, these improve
With the protection domain that retouching is also considered as the embodiment of the present invention.
Divide multiple embodiment that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to
Under specific embodiment.In the range of constant principal right, carrying out change that can be suitable is implemented.
Embodiment of the present invention first aspect provides a kind of compositions of thermosetting resin, in order to solve thermosetting in prior art
Property the problem such as resin combination dielectric properties are poor, heat stability and wet-hot aging performance is poor, curing efficiency is low, processes difference.
First aspect, embodiments provides a kind of compositions of thermosetting resin, comprise diallyl compound with
The prepolymer of maleimide compound, the structural formula of described diallyl compound as the formula (1):
Wherein, R1For-C (CH3)2、-C(CF3)2、-SO2、-CH(CH3)、-CH2Or oxygen atom；R2And R3For identical or different
The aliphatic group of carbon number less than 10 or the aryl radical of carbon number less than 30, and described R2And R3Do not comprise pi-allyl
Group；
The general formula of molecular structure of described maleimide compound is as the formula (2):
In formula, R is aliphatic group or aromatic group, Xa、XbRepresent identical or different hydrogen atom, halogen atom and fat
One in fat race group, m represents the integer of 1 and more than 1.
The compositions of thermosetting resin that embodiment of the present invention first aspect provides, described diallyl compound and Malaysia
The prepolymer of imide compound is to be obtained by reaction with maleimide compound by diallyl compound.Such as formula (2)
Shown diallyl compound has the most volatile characteristic with the prepolymer of maleimide compound, it is ensured that thermosetting
The stability of component ratio in property resin combination, i.e. ensure that the stablizing of dielectric properties of compositions of thermosetting resin, and this is
Because the deviation of any component ratio all can cause the dielectric properties of compositions of thermosetting resin in compositions of thermosetting resin
Difference.It addition, described diallyl compound is little with the prepolymer molecule structural polarity of maleimide compound, therefore have
There are the most excellent dielectric properties, when the cross-linking agent as resin uses, compositions of thermosetting resin excellence can be given
The good performances such as dielectric properties, high-fire resistance, low water absorbable.3rd, described diallyl compound and maleimide
The prepolymer of compound has good solubility property, is difficult in the solution separate out, and has low-down melting viscosity, can
To give the manufacture processing characteristicies such as the good dipping of compositions of thermosetting resin, lamination.4th, described diallyl compound
With the prepolymer of maleimide compound because containing maleimide structure unit, the thermosetting containing this component can be given
The good fire resistance of circuit substrate that resin combination makes, low thermal coefficient of expansion (x, y, z to), good dimensional stability,
High elastic modelling quantity, it is easy to be fabricated to halogen-free copper-clad plate, IC support plate, meets fine-line, the processing of highly dense circuit.
R in described diallyl compound2And R3Do not comprise allyl group, because pi-allyl aryl ether is at high temperature
Claisen can be occurred to reset, generate allyl phenol.
Preferably, described R2And R3Independently selected from methyl, ethyl, propyl group, phenyl, naphthyl, bicyclic pentadiene, hexamethylene
Base, phenethyl, benzyl and to the one in ethenybenzyl.
Described R2And R3One in above-mentioned group not only will not produce Claisen and reset, and Jie that can obtain
Electrical property and reactivity.
It is highly preferred that described R2And R3Independently selected from ethyl with to the one in ethenybenzyl.
Specifically, described diallyl compound can be Anaesthetie Ether diallyl bisphenol, diethyl etherificate diene
Propyl group Bisphenol F, diethyl etherificate diallyl bisphenol S, the methyl etherified diallyl bisphenol of divinylbenzene, divinylbenzene methyl
Etherificate diallyl Bisphenol F or divinylbenzene methyl etherified diallyl bisphenol S etc..
Preferably, described diallyl compound is by described diallyl with the prepolymer of maleimide compound
Compound and described maleimide compound are 90 DEG C～170 DEG C in pre-polymerization temperature, and the pre-polymerization time is 10min's～1080min
Under the conditions of pre-polymerization obtain.
It is highly preferred that pre-polymerization temperature is 120 DEG C～160 DEG C, it is further preferred that pre-polymerization temperature is 130 DEG C～155 DEG C.
Preferably, described diallyl compound is by described diallyl with the prepolymer of maleimide compound
Compound and described maleimide compound in molar ratio 1: (0.05～5) pre-polymerization forms.When molar ratio is more than 1: 0.05,
The thermosetting resin thermostability of reaction prepolymer composition is bad, poor fire；When molar ratio is less than 1: 5, react prepolymer
Storage characteristics bad, maleimide compound easily separates out, and the thermosetting resin poor toughness formed.
It is highly preferred that the prepolymer of described diallyl compound and maleimide compound is by described diallyl
Compound and described maleimide compound 1:(0.4 in molar ratio～2.5) pre-polymerization forms；It is further preferred that described two
Allyl compound is by described diallyl compound and described maleimide with the prepolymer of maleimide compound
Compound 1:(0.5 in molar ratio～2) pre-polymerization forms；It is further preferred that described diallyl compound and maleimide
The prepolymer of amines be by described diallyl compound and described maleimide compound 1:(0.7 in molar ratio～
1.5) pre-polymerization forms.
Preferably, described maleimide compound be selected from phenylmethane list maleimide, N-phenylmaleimide,
N-(2-aminomethyl phenyl) maleimide, N-(4-aminomethyl phenyl) maleimide, N-(2,6-3,5-dimethylphenyl) maleimide
Amine, N-(2,6-diethyl phenyl) maleimide, N-(2-methoxyphenyl) maleimide, diphenyl-methane bismaleimide
Amine, Diphenyl Ether Bismaleimide, diphenyl sulphone (DPS) BMI, N-benzyl maleimide, N-dodecyl maleimide
At least one in amine, N-isopropylmaleimide and N-N-cyclohexylmaleimide.
Preferably, described diallyl compound accounts for described thermosetting resin group with the prepolymer of maleimide compound
The 5%～70% of compound gross weight.When weight content is less than 5%, does not reaches the effect of good crosslinking, thermosetting resin group can be made
The hot property of compound is deteriorated；When more than 70%, processing performance is made to become because the melt viscosity of compositions of thermosetting resin is low again
Difference.It is highly preferred that the prepolymer of described diallyl compound and maleimide compound accounts for the combination of described thermosetting resin
The 15%～55% of thing gross weight.It is further preferred that described diallyl compound and the prepolymer of maleimide compound
Account for the 15%～50% of described compositions of thermosetting resin gross weight.
Preferably, described compositions of thermosetting resin comprises polyphenylene oxide resin, cyanate ester resin, BMI-three
Piperazine resin, 1, at least one thermosetting resin in 2-polybutadiene, butadiene styrene resin and BMI, described thermosetting
Property resin accounts for the 0%～95% of compositions of thermosetting resin gross weight.
Described thermosetting resin makees cross-linking agent with structural formula diallyl compound as the formula (1).
Preferably, described polyphenylene oxide resin is the polyphenylene oxide resin in molecular structure containing unsaturated group, described insatiable hunger
It is vinyl, pi-allyl, acrylate-based or alkynyl with group.
It is further preferred that described polyphenylene oxide resin is number-average molecular weight is 700～8000, molecular end is with unsaturation
The polyphenylene oxide resin of double bond.The number-average molecular weight of described polyphenylene oxide resin more preferably 900～5000, the most preferably
It is 1000～3500.Molecular end has good reactivity with the polyphenylene oxide resin of unsaturated double-bond.Control the number being suitable for
Average molecular weight can provide good dissolubility and low melt viscosity, follow-up impregnation technology operation and lamination flowing
Property, more can improve filler ability in the course of processing of multilayer circuit board.The preferred embodiment for the present invention use dissolubility good,
The low low-molecular-weight end of melting viscosity with the polyphenylene oxide of unsaturated double-bond, and use low-molecular-weight, the most volatile two
Allyl compound makees cross-linking agent, has excellent performance of technical process, it is possible to obtain good-looking is uniform, melt fluidity
Good prepreg and circuit base material.
Described molecular end can be SA9000 (SABIC company) with the polyphenylene oxide resin of unsaturated double-bond, its structure
Formula is as the formula (4)；
Or the polyphenylene oxide resin that structural formula is as the formula (5).
Preferably, the polyphenylene oxide resin containing unsaturated group in described molecular structure accounts for compositions of thermosetting resin gross weight
The 10%～60% of amount.
It is highly preferred that it is total to account for compositions of thermosetting resin containing the polyphenylene oxide resin of unsaturated group in described molecular structure
The 15%～50% of weight.
It is further preferred that the polyphenylene oxide resin containing unsaturated group accounts for thermosetting resin combination in described molecular structure
The 20%～40% of thing gross weight.
Preferably, described cyanate ester resin can be selected from bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanic acid
One or more of ester, bis-phenol M type cyanate, dicyclopentadiene type ethylene rhodanate and phenol type cyanate.
Preferably, described compositions of thermosetting resin further includes machine additive flame retardant, described organic addition type
Fire retardant is phosphorus flame retardant and/or halogenated flame retardant.
Preferably, described organic additive flame retardant accounts for the 5～30% of compositions of thermosetting resin gross weight, more preferably
10～30%, more preferably 10～25%.
It is highly preferred that the heat decomposition temperature that described compositions of thermosetting resin comprises 5% weight portion further is more than or equal to
The bromide fire retardant of 250 DEG C is or/and phosphorus flame retardant, it is further preferred that the heat decomposition temperature comprising 5% weight portion is more than
In the bromide fire retardants of 300 DEG C or/and phosphorus flame retardant.
The most organic additive flame retardant can also and inorganic combustion inhibitor with the use of.Hinder right agent and provide thermosetting resin
Anti-flammability that system is good and thermostability.
Preferably, described halogenated flame retardant is selected from deca-BDE, brominated Polystyrene, brominated polycarbonate, ten bromines two
A kind of or the mixture of at least two in vinylbenzene and the double tetrabromo phthalimide of ethylene.Described mixture such as second
The double tetrabromo phthalimide of support and the mixing of the mixture of TDE, brominated polycarbonate and brominated Polystyrene
The mixture of the double tetrabromo phthalimide of thing, deca-BDE and ethylene, TDE, brominated polycarbonate and bromine
Change the mixture of polystyrene.Described bromide fire retardant can be used alone, it is possible to is used in mixed way, and is used in mixed way and can obtain substantially
Synergy.
Preferably, phosphorus flame retardant is selected from three (2,6-3,5-dimethylphenyl) phosphine, double [two (2, the 6-dimethyl benzenes of resorcinol
Base) phosphate ester], resorcinol tetraphenyldiphosphate, triphenyl phosphate, bisphenol-A double (diphenyl phosphoester), phosphonitrile fire-retardant
Any one or the mixture of at least two in agent and following fire retardant shown in structural formula:
When compositions of thermosetting resin comprises phosphorus flame retardant and the diallyl compound without phenolic hydroxy group and horse
When carrying out the prepolymer of imide compound, it is possible to obtain the halogen-free copper-clad plate that anti-flammability is good, particularly select when phosphorus flame retardant
During with six kinds of fire retardants of above-mentioned molecular structural formula (6)～(11), it is possible to obtain preferably dielectric properties (low-k and low
Dielectric loss angle tangent).In order to obtain more preferably dielectric properties, preferred molecular structure formula (8), the fire retardant of (9).
With organic additive flame retardant with the use of inorganic combustion inhibitor selected from red phosphorus, aluminium hydroxide, magnesium hydroxide or three
The mixture of a kind of or at least two in stibium oxide.The mixture of described mixture such as antimony trioxide and magnesium hydroxide,
Aluminium hydroxide and the mixture of the mixture of the mixture of red phosphorus, antimony trioxide and aluminium hydroxide, magnesium hydroxide and red phosphorus, three oxygen
Change antimony, magnesium hydroxide and the mixture of aluminium hydroxide, the mixture of red phosphorus, antimony trioxide, magnesium hydroxide and aluminium hydroxide.
Preferably, described compositions of thermosetting resin comprises filler and/or curing initiator further.
The thermal coefficient of expansion of compositions of thermosetting resin can be reduced to reduce thermosetting resin group by the use of filler
The laminate of compound making and the probability of the layering plate bursting of printed wiring board, coordinate with fire retardant simultaneously and can also keep thermosetting
The dielectric properties of resin combination are not deteriorated.
Preferably, described filler is selected from aluminium hydroxide, magnesium hydroxide, Kaolin, Pulvis Talci, brucite, calcium silicates, oxidation
Beryllium, boron nitride, glass dust, molten silicon micropowder, ball-shaped silicon micro powder, Firebrake ZB, aluminium nitride, silicon nitride, carborundum, magnesium oxide, oxygen
Change zirconium, aluminium oxide, mullite, Barium metatitanate., barium strontium titanate, rutile titanium dioxide, hollow glass microbead, potassium titanate fibre,
Carborundum mono-crystal fiber, silicon nitride fiber, alumina single crystal fiber, staple glass fibre, polytetrafluorethylepowder powder, polyphenylene sulfide powder
Any one or the mixture of at least two in end and polystyrene powder body.Described mixture such as aluminium hydroxide and hydrogen-oxygen
Change the mixed of the mixture of magnesium, Kaolin and the mixture of the mixture of brucite, calcium silicates and beryllium oxide, boron nitride and glass dust
The mixture of the mixture of the mixture of compound, silicon powder and Firebrake ZB, aluminium nitride and silicon nitride, carborundum and magnesium oxide, oxygen
Change zirconium and the mixture of the mixture of mullite, titanium dioxide and potassium titanate, hollow glass microbead and potassium titanate mono-crystlling fibre
Mixing of mixture, carborundum mono-crystal fiber and the mixture of silicon nitride single crystal fiber, alumina single crystal fiber and staple glass fibre
The mixture of compound, polytetrafluorethylepowder powder and pps powder.Described filler can be used alone, it is possible to is used in mixed way, mixed
Close use and can obtain obvious synergy.
Preferably, in terms of weight content, described filler content in compositions of thermosetting resin is 5～60%；More preferably
Ground, described filler content in compositions of thermosetting resin is 15～55%；It is further preferred that described filler is at thermosetting
Content in resin combination is 20～40%.
Preferably, in the compositions of thermosetting resin of the present invention, also include curing initiator.
In the compositions of thermosetting resin of the present invention, curing initiator plays the effect accelerating reaction, when the present invention's
When compositions of thermosetting resin is heated, curing initiator decomposes generation free radical, causes the strand of resin and cross-linking agent to send out
Raw crosslinking.In terms of weight content, curing initiator content in compositions of thermosetting resin is 1～6%.Curing initiator selects
Benzoyl peroxide, cumyl peroxide, benzoyl peroxide is had by the material of base, preferably curing initiator from being produced from
T-butyl formate, two-(tert-butylperoxyiso-propyl) benzene, 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethylhexane, 2,5-
Two (2-ethyihexanoylperoxy)-2, a kind of or mixture of at least two in 5-dimethyl-3-hexin etc..
Preferably, described compositions of thermosetting resin also includes dyestuff, pigment, surfactant, levelling agent and ultraviolet
Any one or the mixture of at least two in absorbent.
For improving thermostability, caking property etc., it is preferable that described compositions of thermosetting resin also includes polystyrene, benzene second
The block copolymer of alkene-butadiene, the block copolymer of styrene-isoprene, 1,2-polybutadiene, maleic anhydride modified poly-
Butadiene, acrylate modified polybutadiene, epoxide modified polybutadiene, maleic anhydride modified SB
Mixture with a kind of or at least two in acrylate modified SB.
No matter compositions of thermosetting resin of the present invention includes which kind of composition above-mentioned, and described compositions of thermosetting resin is each
The percentage by weight sum of component is 100%.
The compositions of thermosetting resin of the present invention can add solvent and be modulated into glue.Preferably, described solvent is selected from
The combination of a kind of or at least two in ketone, hydro carbons, ethers, esters or aprotic solvent, preferably toluene, dimethylbenzene, first
Alcohol, ethanol, primary alconol, glycol monoethyl ether, propylene glycol monomethyl ether, ethyl acetate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK),
DMF or N, the mixture of a kind of or at least two in N-diethylformamide.Described solvent can be independent
Use, it is possible to be used in mixed way, be used in mixed way and can obtain obvious synergy.The addition of solvent can be according to selected resin
Viscosity determine so as to get the modest viscosity of compositions of thermosetting resin glue, it is simple to coat and impregnate, concrete interpolation
Amount is the present invention be not construed as limiting this.
The compositions of thermosetting resin that embodiment of the present invention first aspect provides, has good heat stability and wet-heat resisting
Property, dielectric constant and dielectric loss angle tangent are low and have excellent processes.
Second aspect, embodiments provides the compositions of thermosetting resin that embodiment of the present invention first aspect provides
Application in resin sheet, resin laminated metal paper tinsel, prepreg, laminate, metal-clad laminate and printed wiring board.
Compositions of thermosetting resin of the present invention is prepared the method for resin sheet and is listed below, but prepares the method for resin sheet not
It is limited to this.Being coated in carrier film by above-mentioned compositions of thermosetting resin, this carrier film can be polyester film or polyimide film, institute
The thickness stating carrier film is 5～150 μm.Then the carrier film being coated with compositions of thermosetting resin adds at 100～250 DEG C
Heat 10 seconds～30 minutes, forms sheet material.The resin sheet thickness formed is in 5～100 μm.
Compositions of thermosetting resin of the present invention is prepared the method for resin laminated metal paper tinsel and is listed below, but it is multiple to prepare resin
The method closing metal forming is not limited only to this.As metal forming, it is possible to use the one or at least two in copper, pyrite, aluminum or nickel
The mixture planted, described metal forming can also use the alloy containing above-mentioned metal.The thickness of metal forming is in 5～150 μm.Pass through
Either manually or mechanically described compositions of thermosetting resin is coated in above-mentioned metal forming by roll-on device.Then this is coated with heat
The metal forming of thermosetting resin compositions is thermally dried so that compositions of thermosetting resin is in semi-cured state (B-
Stage).Then at temperature is 100～250 DEG C, heat time heating time is 10 seconds～30 minutes, solidification, the resin compounded eventually formed
The resin layer thickness of metal is in 1～150 μm.The resin complexes metal copper foil (RCC) obtained by the method can be as printing
Internal layer or the outer layer of wiring board and carry out printed wiring board increasing layer.
The compositions of thermosetting resin of the present invention manufactures the method for prepreg (prepreg, prepreg) and is listed below, so
And the method making prepreg is not limited only to this.Compositions of thermosetting resin glue is immersed on reinforcing material, and to dipping
The preliminary-dip piece having compositions of thermosetting resin is thermally dried so that it is solid that the compositions of thermosetting resin in preliminary-dip piece is in half
In the change stage (B-Stage), prepreg can be obtained.Described heating-up temperature is 80～250 DEG C, the time of described heating be 1～
30min.The reinforcing material wherein used can be inorganic or organic material.Inorganic material is specifiable has glass fibre, carbon fine
The woven fabric of dimension, boron fibre, metal etc. or non-woven fabrics or paper.Glass fabric therein or non-woven fabrics can make E-glass,
Q type cloth, NE cloth, D type cloth, S type cloth, high silica cloth etc..Organic fiber such as polyester, polyamine, polyacrylic acid, polyimides, aramid fiber,
What politef, syndiotactic polytyrene etc. manufactured weaves cotton cloth or non-woven fabrics or paper.But reinforcing material is not limited to this, other can
Reinforcing material for resin tooth equally realizes the present invention.In described prepreg, resin content is between 25～70%.
Laminate, copper-clad laminate, printed wiring board can use above-mentioned resin sheet, resin laminated metal paper tinsel and
Prepared by prepreg.
The method that the prepreg using the present invention above-mentioned prepares laminate is as follows: folded by the prepreg of at least two-layer
Put, and at 130～250 DEG C, 3～50kgf/cm2Under pressure, carry out hot pressing under conditions of hot pressing 60～240min to form lamination
Body, obtains laminate.
The method that the prepreg using the present invention above-mentioned prepares metal-clad laminate is as follows: by one or more pre-
Leaching material is cut into after certain size carries out lamination to send in laminating apparatus and is laminated.Metal forming is placed on prepreg simultaneously
One or both sides, form metal-clad laminate by hot-forming by prepreg compacting.As metal forming, it is possible to use copper,
The mixture of a kind of or at least two in pyrite, aluminum or nickel, described metal forming can also use the conjunction containing above-mentioned metal
Gold.As the pressing conditions of laminate, should select suitably to be laminated solidified bars according to the practical situation of compositions of thermosetting resin
Part.If pressing pressure is too low, can make to exist in laminate space, its electrical property can decline；Lamination pressure is crossed conference and is made lamination
Plate exists too much internal stress so that the dimensional stability of laminate declines, and these are required for by suitably meeting mould
The pressure moulded carrys out pressed sheet to reach required requirement.Usual guideline for conventional neutralizing layer pressing plate is, lamination
Temperature at 130～250 DEG C, pressure 3～50kgf/cm2, hot pressing time 60～240min.
The above-mentioned resin sheet of the present invention, resin laminated metal paper tinsel, prepreg and metal-clad laminate can be used to pass through
Addition or subtractive process prepare the multilayer circuit board of printed wiring board or complexity.
Prepreg of the present invention is used to prepare the method for printed wiring board as follows: to use method as above
Prepare metal-clad laminate, prepared making printed wiring board or the multilayer circuit of complexity by addition process or subtractive process
Plate.
The described the most described compositions of compositions of thermosetting resin glue is added with solvent, carries out institute after solvent adjustment
The liquid glue obtained.
The compositions of thermosetting resin dissolubility that the embodiment of the present invention provides is good, and melting viscosity is low, and storage characteristics is good, has excellent
Good performance of technical process, it is possible to obtain good-looking is uniform, melt fluidity is good prepreg and circuit base material；
The compositions of thermosetting resin that the embodiment of the present invention provides employs the diallyl of the excellent not phenolic hydroxy group of dielectric properties
Compound and the prepolymer of maleimide compound, it is provided that circuit substrate has lower dielectric constant and dielectric loss angle
Tangent；The compositions of thermosetting resin that the embodiment of the present invention provides uses thermostability good and the maleimide of excellent in flame retardance
The prepolymer of compound, it is provided that thermostability that circuit substrate is good and anti-flammability, has high Tg, high Td, low-thermal-expansion system
Number (CTE)；The compositions of thermosetting resin that the embodiment of the present invention provides can use dielectric properties and processing characteristics excellent not
The diallyl compound of phenolic hydroxy group and the prepolymer of maleimide compound, and the tree such as polyphenylene oxide, polyolefin, cyanate
Fat with the use of, make circuit substrate obtain better low-k and low dielectric loss angle tangent value, high elastic modulus,
Low water absorption rate, better anti-flammability.
Compositions of thermosetting resin of the present invention is except can serve as preparing resin sheet, resin laminated metal paper tinsel, pre-
Outside leaching material, laminate, metal-clad laminate, printed wiring board, it may also be used for be used for preparing adhesive, coating, it is also possible to
In building, aviation, boats and ships, auto industry.
Embodiment 1
Adding water 3000g, sodium hydroxide 30g in four-hole boiling flask, temperature adds diallyl bis-phenol after reducing to room temperature
A95g, is placed in this solution in cryosel bath, treats that temperature is down to less than 20 DEG C, start to drip bromic ether 150g, control temperature low
In 20 DEG C, low-temp reaction 30min after completion of dropwise addition, rise high-temperature and react 2h, stopped reaction, cooling, split-phase to 50 DEG C, wash
It is etherified diallyl bisphenol to ethyl.
Taking the ethyl etherificate diallyl bisphenol 1mol of above synthesis, diphenyl methane dimaleimide 1mol part is put into
In flask, it is heated to 145 DEG C, stirs 30 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol and diphenyl-methane
The prepolymer of BMI.
Fig. 1 is the ethyl etherificate diallyl bisphenol prepolymer with diphenyl methane dimaleimide of above synthesis
Infrared spectrogram.
Take the prepolymer 50 parts of ethyl etherificate diallyl bisphenol and the diphenyl-methane maleimide of above synthesis, 15
Part TDE, 33 parts of molten silicon micropowders, 2 parts of cumyl peroxides, use toluene to be dissolved by above-claimed cpd, and adjust
Make the glue of appropriate viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove solvent,
Obtain the B-stage prepreg test sample that resin content is 54%.
The prepreg of eight above-mentioned preparations and the electrolytic copper foil of two panels half ounce are superimposed together, are carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is as follows: lamination is as follows: 1, material temperature is when 80～120 DEG C, and heat up speed
Degree controls at 1.0～3.0 DEG C/min；2, pressure is set to 20kg/cm2；3, solidification temperature 190 DEG C, and keep this temperature 90 points
Clock.Gained doublesided copperclad laminate is carried out physical property measurement, and respective performances is shown in Table 1.
Embodiment 2
Ethyl etherificate the diallyl bisphenol 1mol, diphenyl sulphone (DPS) BMI 0.5mol of Example 1 synthesis put into
In flask, it is heated to 140 DEG C, stirs 90 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol double with diphenyl sulphone (DPS)
The prepolymer of maleimide.
Take the ethyl etherificate diallyl bisphenol of above synthesis and the prepolymer 30 parts of diphenyl sulphone (DPS) BMI, point
Sub-end is with the polyphenylene oxide resin (SA9000) 30 parts of unsaturated double-bond, bisphenol A cyanate ester 16 parts, 12 parts of decabrominated dipheny second
Alkane, 25 parts of molten silicon micropowders, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene by above-mentioned
Compound dissolution, and it is modulated into the glue of appropriate viscosity.2116 type E-glass cloth are used to infiltrate this glue, and at 135 DEG C
In baking oven, remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The prepreg of eight above-mentioned preparations and the electrolytic copper foil of two panels half ounce are superimposed together, are carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 1.
Embodiment 3
Ethyl etherificate the diallyl bisphenol 1mol, diphenyl sulphone (DPS) BMI 0.5mol of Example 1 synthesis put into
In flask, it is heated to 140 DEG C, stirs 90 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol double with diphenyl sulphone (DPS)
The prepolymer of maleimide.
Take the ethyl etherificate diallyl bisphenol of above synthesis and the prepolymer 30 parts of diphenyl sulphone (DPS) BMI, point
Sub-end with 30,12 parts of TDEs of polyphenylene oxide resin (SA9000) of unsaturated double-bond, 25 parts of molten silicon micropowders, 2
Part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene to be dissolved by above-claimed cpd, and be modulated into
The glue of appropriate viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove solvent, it is thus achieved that
Resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels half ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 1.
Embodiment 4
The ethyl etherificate diallyl bisphenol 1mol of Example 1 synthesis, diphenyl methane dimaleimide 1.2mol part
Put in flask, be heated to 155 DEG C, stir 60 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol and hexichol
The prepolymer of methane BMI.
Take the ethyl etherificate diallyl bisphenol of above synthesis and the prepolymer 30 parts of diphenyl methane dimaleimide,
Butadiene styrene resin 30 parts (Sartomer ricon100, lower same), 25 parts of double tetrabromo phthalimides of ethylene, 23 parts of molten silicons
Micropowder, uses toluene to be dissolved by above-claimed cpd, and is modulated into the glue of appropriate viscosity by 2 part two-(tert-butylperoxyiso-propyl) benzene
Water.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove solvent, it is thus achieved that resin content is
The B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 1.
Embodiment 5
The ethyl etherificate diallyl bisphenol 1mol of Example 1 synthesis, phenylmethane list maleimide 1mol part is put into
In flask, it is heated to 140 DEG C, stirs 90 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol and phenylmethane list
The prepolymer of maleimide.
Take the ethyl etherificate diallyl bisphenol of above synthesis and the prepolymer 17 parts of phenylmethane list maleimide, point
Phosphate ester shown in sub-end 30,25 parts of structural formulas (8) of polyphenylene oxide resin (SA9000) with unsaturated double-bond, 25 parts melt
Silicon powder, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene to be dissolved by above-claimed cpd,
And it is modulated into the glue of appropriate viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove
Solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 1.
Comparative example 1
Taking diallyl bisphenol 100 parts, diphenyl methane dimaleimide 105 parts is put in flask, is heated to 155 DEG C,
Stir 30 minutes, pour out cooling, i.e. obtain the prepolymer of diallyl bisphenol and diphenyl methane dimaleimide.
Take the diallyl bisphenol of above synthesis and the prepolymer 50 parts of diphenyl methane dimaleimide, 15 part of ten bromine
Diphenylethane, 33 parts of molten silicon micropowders, 2 parts of cumyl peroxides, use toluene to be dissolved by above-claimed cpd, and be modulated into conjunction
The glue of suitable viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove solvent, it is thus achieved that tree
Fat content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 1.
Comparative example 2
Taking diallyl bisphenol 100 parts, diphenyl sulphone (DPS) BMI 45 parts is put in flask, is heated to 140 DEG C, stirs
Mix 90 minutes, pour out cooling, i.e. obtain the prepolymer of diallyl bisphenol and diphenyl sulphone (DPS) BMI.
Take the diallyl bisphenol of above synthesis and the prepolymer 17 parts of diphenyl sulphone (DPS) BMI, molecular end band
There is a phosphate ester shown in 30,25 parts of structural formulas (8) of polyphenylene oxide resin (SA9000) of unsaturated double-bond, 25 parts of molten silicon micropowders, 2
Part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene to be dissolved by above-claimed cpd, and be modulated into
The glue of appropriate viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove solvent, it is thus achieved that
Resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 1.
Table 1
Note 1:
1. in table one, each constituent content is all remembered with weight portion；
2.SA9000 be the polyphenylene oxide resin of sabic company；
3.CE is bisphenol A cyanate ester；
4.SC2050MB be the silicon dioxide of admatechs company.
Note 2:
1. glass transition temperature (Tg): use DSC test, tests according to the DSC of IPC-TM-6502.4.25 defined
Method is measured.
2. peel strength is tested according to " after the thermal stress " experiment condition in IPC-TM-6502.4.8 method.
3. dielectric constant (DK) and dielectric loss factor (DF): test according to the method for IPC-TM-6502.5.5.13 defined.
The most resistance to dip solderability evaluation: copper-clad laminate is immersed in the stannum stove that temperature is 288 DEG C took out after 20 seconds cold
But to room temperature, it is impregnated into the most again in stannum stove 5 times repeatedly, resistance to dip solderability by observing ocular estimate.
Resistance to dip solderability evaluation after 5.PCT: be immersed in copper etchant solution by copper-clad laminate, removes surface Copper Foil and evaluates base
Plate.Place a substrate in steam pressure cooker, at 121 DEG C, after processing 2 hours under 2atm, be immersed in the stannum stove that temperature is 288 DEG C
In, record the corresponding time when base material occurs and bubbles or divide.When base material did not the most occur more than 5 minutes bubbling in stannum stove
Or layering can terminate to evaluate.
6.Td: be immersed in copper etchant solution by copper-clad laminate, removes surface Copper Foil and evaluates substrate.Substrate is used heat
Zero-g aircraft instrument (TGA) is tested, and in blanket of nitrogen, heats up with 10 DEG C/min, reaches temperature value during 5% weight loss.
7.CTE: use TMA test, 10 DEG C/min of programming rate.
From embodiment 1～5 with comparative example 1～2 it may be seen that embodiment 1～5 gained doublesided copperclad laminate is relative right
Ratio 1～2 has lower dielectric loss angle tangent and lower water absorption rate, and this is two allyls used due to comparative example 1～2
Base phenolic compound contains the phenolic hydroxyl group that polarized is big, and the copper-clad plate dielectric constant therefore made and dielectric loss angle tangent are bigger.
And the existence of phenolic hydroxyl group, the curing efficiency of resin compound is low, and completing solidification needs the high temperature of more than 220 DEG C, and longer
Hardening time, and the diallyl phenolic compound that embodiment 1～5 uses, its phenolic hydroxyl group has the most been etherified, and can be effectively improved
Problem present in comparative example.It addition, from embodiment 5 it can be seen that when whole system without halogen time, it is also possible to obtain good
The combination properties such as good dielectric properties, are suitable for making halogen-free copper-clad plate；And embodiment 2 is adapted for use as IC base plate for packaging.
Embodiment 6
Adding water 3000g, sodium hydroxide 30g in four-hole boiling flask, temperature adds diallyl bis-phenol after reducing to room temperature
A95g, is placed in this solution in cryosel bath, treats that temperature is down to less than 20 DEG C, start to drip p-chloromethyl styrene 180g, control
Temperature is less than 20 DEG C, low-temp reaction 30min after completion of dropwise addition, rises high-temperature and reacts 2h, stopped reaction to 50 DEG C, lowers the temperature, split-phase,
Washing obtains p-methylstyrene etherificate diallyl bisphenol.
Take methyl styrene etherificate the diallyl bisphenol 1mol, diphenyl methane dimaleimide 1mol of above synthesis
Put in flask, be heated to 145 DEG C, stir 30 minutes, pour out cooling, i.e. obtain methyl styrene etherificate diallyl bisphenol
Prepolymer with diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer of diphenyl methane dimaleimide
50 parts, 15 parts of TDEs, 33 parts of molten silicon micropowders, 2 parts of cumyl peroxides, use toluene that above-claimed cpd is molten
Solve, and be modulated into the glue of appropriate viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove
Remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 2.
Embodiment 7
The methyl styrene etherificate diallyl bisphenol 1mol of Example 6 synthesis, diphenyl methane dimaleimide
4mol puts in flask, is heated to 135 DEG C, stirs 120 minutes, pours out cooling, i.e. obtains methyl styrene etherificate diallyl
Bisphenol-A and the prepolymer of diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer of diphenyl methane dimaleimide
45 parts, bisphenol A cyanate ester 16 parts, 14 parts of TDEs, 25 parts of ball-shaped silicon micro powders, appropriate zinc octoate, use butanone
Above-claimed cpd is dissolved, and is modulated into the glue of appropriate viscosity.2116 type E-glass cloth are used to infiltrate this glue, and
In 155 DEG C of baking ovens, remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 2.
Embodiment 8
The methyl styrene etherificate diallyl bisphenol 1mol of Example 6 synthesis, diphenyl methane dimaleimide
0.5mol puts in flask, is heated to 140 DEG C, stirs 90 minutes, pours out cooling, i.e. obtains methyl styrene etherificate diallyl
Bisphenol-A and the prepolymer of diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer of diphenyl methane dimaleimide
30 parts, molecular end is with 30,13 parts of TDEs of polyphenylene oxide resin (SA9000) of unsaturated double-bond, 25 parts of molten silicons
Micropowder, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene to be dissolved by above-claimed cpd, and
It is modulated into the glue of appropriate viscosity.Use 2116 type E-glass cloth to infiltrate this glue, and in 135 DEG C of baking ovens, remove molten
Agent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 2.
Embodiment 9
The methyl styrene etherificate diallyl bisphenol 1mol of Example 6 synthesis, diphenyl methane dimaleimide
2mol puts in flask, is heated to 155 DEG C, stirs 60 minutes, pours out cooling, i.e. obtains methyl styrene etherificate diallyl double
Phenol A and the prepolymer of diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer 30 of diphenyl methane dimaleimide
Part, butadiene styrene resin 30 parts, 25 parts of double tetrabromo phthalimides of ethylene, 23 parts of molten silicon micropowders, 2 part two-(t-butyl peroxy
Isopropyl) benzene, use toluene to be dissolved by above-claimed cpd, and be modulated into the glue of appropriate viscosity.Use 2116 type electron level glass
Glass cloth infiltrates this glue, and in 135 DEG C of baking ovens, removes solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 2.
Embodiment 10
The methyl styrene etherificate diallyl bisphenol 1mol of Example 6 synthesis, diphenyl methane dimaleimide
0.5mol puts in flask, is heated to 140 DEG C, stirs 90 minutes, pours out cooling, i.e. obtains methyl styrene etherificate diallyl
Bisphenol-A and the prepolymer of diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer of diphenyl methane dimaleimide
18 parts, the phosphate ester shown in molecular end 30,25 parts of structural formulas (8) of polyphenylene oxide resin (SA9000) with unsaturated double-bond,
25 parts of molten silicon micropowders, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene by above-mentioned chemical combination
Thing dissolves, and is modulated into the glue of appropriate viscosity.2116 type E-glass cloth are used to infiltrate this glue, and at 135 DEG C of baking ovens
In, remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 2.
Table 2
Embodiment 11
The ethyl etherificate diallyl bisphenol 1mol of Example 1 synthesis, diphenyl methane dimaleimide 3.5mol part
Put in flask, be heated to 135 DEG C, stir 120 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol and hexichol
The prepolymer of methane BMI.
Take the ethyl etherificate diallyl bisphenol of above synthesis and the prepolymer 25 parts of diphenyl methane dimaleimide,
Bisphenol A cyanate ester 16 parts, molecular end is with the polyphenylene oxide resin (SA9000) 20 parts of unsaturated double-bond, 14 parts of decabrominated diphenies
Ethane, 25 parts of ball-shaped silicon micro powders, appropriate zinc octoate, use butanone to be dissolved by above-claimed cpd, and be modulated into appropriate viscosity
Glue.Use 2116 type E-glass cloth to infiltrate this glue, and in 155 DEG C of baking ovens, remove solvent, it is thus achieved that resin content is
The B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 3.
Embodiment 12
Ethyl etherificate the diallyl bisphenol 1mol, diphenyl methane dimaleimide 0.5mol of Example 1 synthesis are put
Enter in flask, be heated to 140 DEG C, stir 90 minutes, pour out cooling, i.e. obtain ethyl etherificate diallyl bisphenol and hexichol first
The prepolymer of alkane BMI.
Take the ethyl etherificate diallyl bisphenol of above synthesis and the prepolymer 20 parts of diphenyl methane dimaleimide,
Molecular end with the polyphenylene oxide resin (SA9000) 30 parts of unsaturated double-bond, butadiene styrene resin 10 parts, 13 parts of TDEs,
25 parts of molten silicon micropowders, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin, use toluene by above-mentioned chemical combination
Thing dissolves, and is modulated into the glue of appropriate viscosity.2116 type E-glass cloth are used to infiltrate this glue, and at 135 DEG C of baking ovens
In, remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 3.
Embodiment 13
The methyl styrene etherificate diallyl bisphenol 1mol of Example 6 synthesis, diphenyl methane dimaleimide
1.5mol part is put in flask, is heated to 155 DEG C, stirs 60 minutes, pours out cooling, i.e. obtains methyl styrene and be etherified two allyls
Base bisphenol-A and the prepolymer of diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer of diphenyl methane dimaleimide
22 parts, molecular end is with the polyphenylene oxide resin (SA9000) 15 of unsaturated double-bond, bisphenol A cyanate ester 16 parts, 20 parts of structures
Phosphate ester shown in formula (8), 25 parts of ball-shaped silicon micro powders, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin,
Use toluene to be dissolved by above-claimed cpd, and be modulated into the glue of appropriate viscosity.2116 type E-glass cloth are used to infiltrate this
Glue, and in 135 DEG C of baking ovens, remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 3.
Embodiment 14
The methyl styrene etherificate diallyl bisphenol 1mol of Example 6 synthesis, diphenyl methane dimaleimide
0.05mol puts in flask, is heated to 140 DEG C, stirs 90 minutes, pours out cooling, i.e. obtains methyl styrene and be etherified two allyls
Base bisphenol-A and the prepolymer of diphenyl methane dimaleimide.
Take the methyl styrene etherificate diallyl bisphenol of above synthesis and the prepolymer of diphenyl methane dimaleimide
18 parts, molecular end is with the polyphenylene oxide resin (SA9000) 30 parts of unsaturated double-bond, butadiene styrene resin 10 parts, 25 parts of structural formulas
(12) phosphate ester shown in, 15 parts of ball-shaped silicon micro powders, 2 part 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethyl-3-hexin,
Use toluene to be dissolved by above-claimed cpd, and be modulated into the glue of appropriate viscosity.2116 type E-glass cloth are used to infiltrate this
Glue, and in 135 DEG C of baking ovens, remove solvent, it is thus achieved that resin content is the B-stage prepreg test sample of 54%.
The electrolytic copper foil of eight prepregs and two panels one ounce is superimposed together, carries out lamination by hot press and obtain double
Face copper-clad laminate.Lamination is with embodiment 1, and respective performances is shown in Table 3.
Table 3
Claims (13)
1. a compositions of thermosetting resin, it is characterised in that comprise diallyl compound and maleimide compound
Prepolymer, shown in the structural formula of described diallyl compound such as formula (1):
Wherein, R1For-C (CH3)2、-C(CF3)2、-SO2、-CH(CH3)、-CH2Or oxygen atom；Described R2And R3Independently selected from benzene
Base, naphthyl, bicyclic pentadiene, phenethyl, benzyl and to the one in ethenybenzyl；
Shown in the general formula of molecular structure of described maleimide compound such as formula (2):
In formula, R is aliphatic group or aromatic group, Xa、XbRepresent identical or different hydrogen atom, halogen atom and aliphatic
One in group, m represents the integer of 1 and more than 1.
2. compositions of thermosetting resin as claimed in claim 1, it is characterised in that described diallyl compound and maleoyl
The prepolymer of group with imine moiety is to be 90 by described diallyl compound and described maleimide compound in pre-polymerization temperature
DEG C～170 DEG C, the pre-polymerization time is that pre-polymerization obtains under conditions of 10min～1080min.
3. compositions of thermosetting resin as claimed in claim 1 or 2, it is characterised in that described diallyl compound and horse
Carrying out the prepolymer of imide compound is by described diallyl compound and described maleimide compound in molar ratio 1:
(0.05～5) pre-polymerization forms.
4. compositions of thermosetting resin as claimed in claim 3, it is characterised in that described diallyl compound and maleoyl
The prepolymer of group with imine moiety is by described diallyl compound and described maleimide compound 1:(0.4 in molar ratio
～2.5) pre-polymerization forms.
5. compositions of thermosetting resin as claimed in claim 1, it is characterised in that described maleimide compound is selected from
Phenylmethane list maleimide, N-phenylmaleimide, N-(2-aminomethyl phenyl) maleimide, N-(4-aminomethyl phenyl) horse
Come acid imide, N-(2,6-3,5-dimethylphenyl) maleimide, N-(2,6-diethyl phenyl) maleimide, N-(2-methoxy
Base phenyl) maleimide, diphenyl methane dimaleimide, Diphenyl Ether Bismaleimide, diphenyl sulphone (DPS) BMI,
N-benzyl maleimide, N-dodecyl maleimide, N-isopropylmaleimide and N-N-cyclohexylmaleimide
In at least one.
6. compositions of thermosetting resin as claimed in claim 1, it is characterised in that described diallyl compound and maleoyl
The prepolymer of group with imine moiety accounts for the 5%～70% of described compositions of thermosetting resin gross weight.
7. compositions of thermosetting resin as claimed in claim 6, it is characterised in that described diallyl compound and maleoyl
The prepolymer of group with imine moiety accounts for the 15%～55% of described compositions of thermosetting resin gross weight.
8. compositions of thermosetting resin as claimed in claim 1, it is characterised in that described compositions of thermosetting resin is further
Comprise polyphenylene oxide resin, cyanate ester resin, bismaleimide-triazine resin, 1,2-polybutadiene, butadiene styrene resin and double
At least one thermosetting resin in maleimide, described thermosetting resin accounts for the 0% of compositions of thermosetting resin gross weight
～95%.
9. compositions of thermosetting resin as claimed in claim 8, it is characterised in that described polyphenylene oxide resin is in molecular structure
Containing the polyphenylene oxide resin of unsaturated group, described unsaturated group is vinyl, pi-allyl, acrylate-based or alkynyl.
10. compositions of thermosetting resin as claimed in claim 9, it is characterised in that containing unsaturation in described molecular structure
The polyphenylene oxide resin of group accounts for the 10%～60% of compositions of thermosetting resin gross weight.
11. compositions of thermosetting resin as claimed in claim 1, it is characterised in that further include machine additive flame retardant
Agent, described organic additive flame retardant is phosphorus flame retardant and/or halogenated flame retardant.
12. compositions of thermosetting resin as claimed in claim 1, it is characterised in that comprise filler further and/or solidification is drawn
Send out agent.
13. compositions of thermosetting resin as described in any one of claim 1～12 resin sheet, resin laminated metal paper tinsel,
Application in prepreg, laminate, metal-clad laminate and printed wiring board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310703411.2A CN103756315B (en) | 2013-12-19 | A kind of compositions of thermosetting resin and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310703411.2A CN103756315B (en) | 2013-12-19 | A kind of compositions of thermosetting resin and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103756315A CN103756315A (en) | 2014-04-30 |
| CN103756315B true CN103756315B (en) | 2016-11-30 |
Family
ID=
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Effective date of registration: 20210428 Address after: Unit 3401, unit a, building 6, Shenye Zhongcheng, No. 8089, Hongli West Road, Donghai community, Xiangmihu street, Futian District, Shenzhen, Guangdong 518040 Patentee after: Honor Device Co.,Ltd. Address before: 518129 Bantian HUAWEI headquarters office building, Longgang District, Guangdong, Shenzhen Patentee before: HUAWEI TECHNOLOGIES Co.,Ltd. |